固液界面吸附活化能的测定及其原理

固液界面吸附动力学机理的研究对深入了解吸附规律具有重要意义.艾宏韬曾提出吸附动力学的基本公式,但对活化能的研究未予重视.陈松等虽测定了水合氧化钛在海水中吸附铀的活化能,但均假设吸附反应仅是单向进行.本文从质量作用定律出发,对正反两方向的反应速率及吸附剂、吸附质的有关参数均予以考虑,导出了分别适用于速率较小或较大两种情况下活化能的实验测定方法,并分别以水合氧化钛在海水中吸附铀及水合氧化铁吸附铅、铜的动力学实验结果为例,加以验证.     

粒度不均一交换剂的离子交换反应动力学(Ⅰ)——粒内扩散或液膜扩散控制反应速度的同位素交换反应

本文研究了包含不同半径离子交换剂体系的同位素交换反应动力学。对于粒内扩散和液膜扩散控制反应速度的不均一体系,导出了表述离子交换剂和有限浴溶液中离子之间异相同位素交换反应交换度。     

大孔吸附树脂对邻甲酚的吸附行为研究

研究了大孔吸附树脂NDA—909吸附水溶液中邻甲酚的热力学特征，并与Amberlite XAD—4树脂进行了比较．通过吸附动力学实验，初步探讨了初始温度对吸附过程的影响。结果表明，NDA—909对邻甲酚的吸附符合Freundlich经验公式，表现为放热的物理吸附过程．此外吸附速率受颗粒内扩散和其它类型扩散的共同控制。     

离子交换平衡和动力学的研究(Ⅲ) Y~(3+)-H~+交换平衡和动力学

用强酸性阳离子交换树脂研究了Y~(3+)-H~+交换反应的平衡和动力学,测定了反应的等温线,求得合理热力学平衡常数Ka=1.9×10~2。实验表明,正交换反应RH/Y~(3+)符合一般规律,即在低浓度时,系液膜扩散机理,高浓度时,系粒内扩散机理;而逆交换反应R_3Y/H~+在本实验的浓度和搅拌速度下,均为粒内扩散机理。正逆交换反应机理的差别是树脂对三价稀土元素Y~(3+)具有极高的亲和性所致。估算了液膜互扩散系数与液膜厚度的比值。用电子计算机求算了随交换剂组成变化的积分粒内互扩散系数。     

大孔树脂对红霉素的吸附动力学研究

利用大孔吸附树脂Amberlite XAD16及HZ816对红霉素的吸附动力学实验,研究了温度、初始浓度、溶液pH值及搅拌速度等因素对吸附过程的影响.结果表明,Amberlite XAD16及HZ816对红霉素的吸附速率符合一级吸附动力学方程及颗粒内扩散方程,过程受液膜扩散阻力及颗粒内扩散阻力共同影响.同时,表观吸附速率常数与颗粒内扩散速率常数均随着温度的升高而增大,随着初始浓度的增大而增大,随着溶液pH值增大而增大,随着搅拌速度加快而增大.     

胡芦巴总皂苷在HPD 400A大孔树脂上的吸附性能研究

静态条件下,对胡芦巴中总皂苷在HPD 400A树脂的吸附平衡、吸附动力学、热力学进行了深入探讨,测定了不同温度下胡芦巴中总皂苷在该树脂上的吸附等温线,吸附动力学曲线以及热力学参数。结果表明,Freundlich方程可较好地描述胡芦巴中总皂苷在该树脂上的吸附平衡;吸附动力学规律可用二级速率方程表示,液膜扩散和颗粒内扩散是吸附的主要速率控制步骤,吸附活化能为8.314kJ/mol;热力学参数表明此吸附过程为吸热过程。     

氨基酸螯合吸附树脂对苯酚的吸附行为研究

合成了一种L-酪氨酸修饰的螯合吸附树脂(AJS-02),并与超高交联树脂NDA-150作对比,研究了其对苯酚的吸附和脱附行为.静态实验结果表明,在研究的浓度范围内,吸附平衡数据符合Langmuir等温吸附方程且吸附为放热过程.溶液的初始浓度为100 mg/L、吸附温度为288 K时,苯酚在AJS-02和NDA-150上的平衡吸附量分别为76.98和91.97 mg/g,苯酚在两种树脂上的吸附是比表面积和表面官能团共同作用的结果.动力学数据表明吸附动力学符合液膜扩散方程和颗粒内扩散方程,液膜扩散为吸附速率的主要控制步骤.动态吸附-脱附实验表明,AJS-02树脂对苯酚的动态穿透吸附量和饱和吸附量分别为5.26×10-2和6.60×10-2mmol/mL,采用95%乙醇作脱附剂,脱附率可达91.5%以上.     

胸腺五肽在NH-1树脂上的离子交换过程研究

研究了胸腺五肽(TP5)在NH-1树脂上的离子交换过程.结果表明,在pH 2.O的条件下,其等温吸附过程符合Langmuir等温吸附方程,最大吸附量为221.07mg/g wet resin;静态吸附动力学的研究结果显示,NH-1树脂对TP5的吸附过程主要受颗粒扩散控制影响,TP5的颗粒内扩散系数为4.50×10-9cm2/s;对比Nernst-Planck与Fick动力学模型,可用Fick动力学模型来描述TP5在NH-1树脂内的颗粒扩散行为,其有效扩散系数为5.58×10-9cm2/s;采用固定床吸附数学模型,对TP5离子交换柱行为进行模拟,该数学模型考虑了颗粒扩散、轴向返混、非线性平衡以及液膜扩散.结果显示,模拟数据与实验结果具有较好的符合.     

黄姜黄色素在大孔树脂上的吸附动力学研究

采用静态法考察了8种大孔吸附树脂对黄姜黄色素的吸附及解吸特性,筛选出LX-18G树脂具有较高的吸附选择性和良好的脱附性能.以LX-18G树脂对黄姜色素的吸附平衡和吸附动力学进行了深入探讨,测定了不同温度下黄姜色素在该树脂上的吸附等温线,以及不同温度,初始液浓度和转速下的吸附动力学曲线.结果表明,Langmuir方程可更好地描述黄姜色素在该树脂上的吸附平衡.吸附动力学规律可用二级速率方程表示,液膜扩散和颗粒内扩散分别是吸附初期和吸附后期的主要速率控制步骤,吸附活化能为5.37kJ/mol.     

ZnO/C纳米球的亚甲基蓝单吸附特性:平衡、动力学及机理（英文）

采用电弧放电法制备了Zn O/C纳米球,利用FESEM、XRD和N2吸附/脱附测试进行了表征。在避光条件下研究了复合材料对亚甲基蓝的吸附性能。研究结果表明,随着亚甲基蓝的浓度及接触时间的增长吸附量明显上升,在吸附时间为150 min时达到吸附平衡。采用Langmuir、Freundlich及Temkin等温吸附模式对吸附平衡进行了研究。结果表明,吸附等温线符合Langmuir等温吸附模式,单层吸附饱和容量可达188.68 mg·g-1。利用动力学模型、内扩散模型和外扩散速率控制模型拟合实验数据,拟合数据表明其动力学符合伪二级动力学模型;内扩散机理不是吸附速率的唯一限制机理,亚甲基蓝的总吸附速率受膜扩散控制。     

磷酸可待因在安伯来特IRP-69上的离子交换平衡特性研究

采用批式离子交换法研究了磷酸可待因在安伯来特IRP-69上的离子交换平衡特性、动力学及热力学特征.结果表明,在3个温度(298K、308K和318K)及研究的浓度范围内,离子交换吸附等温方程和Freundlich方程都能够对磷酸可待因在安伯来特IRP-69上的离子交换平衡等温线进行很好的拟合,其离子交换动力学特征基本符合二级动力学方程.磷酸可待因在安伯来特IRP-69上的离子交换行为的热力学参数(ΔH、ΔG、ΔS)都小于0.在3个温度(298K、308K和318K)下,同一初始浓度(350mmol/L)的磷酸可待因在安伯来特IRP-69上的平衡交换吸附量分别为1.1295mmol/g、1.1203 mmol/g和1.1129 mmol/g.     

模拟磷矿脱镁废水中镁离子的交换动力学研究

用动边界模型积分方程描述模拟磷矿脱镁废水中Mg2＋在001×7×7型树脂上的有限浴交换动力学,得到了动力学总方程.Mg2＋的交换过程属颗粒扩散控制,表观活化能为23.45 kJ•mol－1,Mg2＋的表观反应级数为0.68.     

The kinetics and mechanism of bromide ion isotope exchange reaction in strongly basic anion-exchange resin duolite A-162 determined by the radioactive tracer technique

In the present investigation, ⁸²Br radioactive isotope was used as a tracer to study the kinetics and mechanism of exchange reaction between an ion exchange resin and an external bromide ion solution. In an attempt to study the reversible bromide ion isotopic exchange reaction kinetics, it was expected that whether the initial step was the exchange of radioactive bromide ions from the solution into the ion exchange resin (forward reaction) or from the ion exchange resin into the solution (reverse reaction), two ion isotopic exchange reactions should occur simultaneously, which was further confirmed by the experimental specific reaction rates of 0.130 and 0.131 min⁻¹, respectively. The results can be used to standardize process parameters so as to optimize the utilization of ion exchange resins in various industrial applications. The text was submitted by the authors in English.     

The application of the radioactive tracer technique to study the kinetics of bromide isotope exchange reaction with the participation of strongly basic anion exchange resin indion FF-IP

In the present investigation, the ⁸²Br radioactive isotope was used as a tracer to study the kinetics and mechanism of the exchange reaction between an ion exchange resin and an external solution of bromide ions. In an attempt to study the reversible bromide isotope exchange reaction kinetics, it was expected that whether the initial step was the exchange of radioactive bromide ions from the solution to the ion exchange resin (forward reaction) or from the ion exchange resin to the solution (reverse reaction), the two ion-isotope exchange reactions should occur simultaneously, which was further confirmed by the experimental values of specific reaction rates, 0.142 and 0.141 min⁻¹, respectively. The results will be useful to standardize the process parameters so as to achieve optimum use of ion exchange resins in various industrial applications. The text was submitted by the authors in English.     

稀土离子在多孔阳离子交换剂内的扩散动力学

研究了稀土离子在Amberlyst15、D001、XN1010多孔树脂内的自扩散。结果表明,扩散过程遵循二级分散扩散机制。用粒内扩散方程求算了有效粒内扩散系数e,将e分解为树脂孔道扩散系数p及树脂固相扩散系数s,p与该离子在外部溶液中的自扩散系数相近,而s接近于与实验用的多孔树脂交联度相同的凝胶树脂内的自扩散系数值。     

Volumes of solid state ions and their estimation

Formula unit volume, Vm, has recently been identified as the key link to a number of thermodynamic functions and has given rise to an alternative approach to thermodynamics for modern inorganic materials (volume-based thermodynamics, VBT). In an earlier publication, we reported over 400 ion volumes for commonly encountered cations and anions derived from crystal structure data which can, in turn, be used to generate formula unit volumes for those ionic salts, for which crystal structure data, which is the preferred source of such volume data, is not available. The purpose of the present paper is to report a further 147 supplementary ion volumes. These are compared to ion volumes obtained from the summation of Hofmann's elemental volumes, a convenient and alternative approach for the estimation of Vm. It is shown that many elusive ion volumes can be estimated using these databases in tandem by adopting the newly proposed isomegethic rule and other volume additivity rules. Generation of volume data for new, hypothetical, and counterintuitive ions, as well as for traditional ions, is now a reality, as is demonstrated.     

离子交换树脂吸附镉的动力学研究

实验采用离子交换法吸附氯盐体系中的镉,用动态法对2017型强碱性阴离子交换树脂的工作条件进行了优化,在最佳反应体系下,用批式离子交换法研究了温度、溶液浓度和树脂粒径对交换过程的影响,并用动边界模型描述交换过程的动力学,确定了离子交换行为的速度控制步骤为颗粒扩散,并推算出了交换过程的表观活化能、反应级数、速率常数和动力学总方程式。     

INTRAPARTICLE DIFFUSION OF RARE EARTHS IN POROUS CATION EXCHANGERS

Experiments for determining cerium isotope ion exchange rates with macroporous resins Amberlyst 15,D001 and XN1010 are discribed.The kinetics of the isotope ion exchange reaction has been examined by a simple theoretical equation of intraparticle effective diffustivity De in a porous ion exchanger.The ion exchange proceedes by diffusion within the macropores and the solid phase of the resin,De of cerium was affected by the concentration of the bulk solution C and was separated into a macropore diffusivity D^-p and a solid phase diffusivity D^-g by the equation.The diffusion coefficients of the exchanging ion are shown to have the values in the macropores comparable with those in the bulk solution and to have the values in the solid phase comparable with those in gel resin with the same crosslinkage as the resins used for the experiments.     

A new experimental technique for validating exchange models of carbon dioxide between the atmosphere and sea-water

The mechanism of CO₂-exchange between the atmosphere and sea-water was re-examined by simultaneously measuring pH and pO₂ in artificial sea-water exposed to CO₂ and air atmospheres. The data were fitted to an exchange model by using both the differential and integral forms of the diffusion equation. It was found that the pH and pO₂ data support the assumption that the exchange for these gases is driven by the gradient of the partial pressure of the gas across the imaginary solution-gas boundary layer (the z layer) and is not affected by chemical reaction or hydration rate under the experimental conditions used, viz. 1–100 meq/l., alkalinity, pH 4.5–8.3 and z-layer thickness 2–500 μm. It is concluded that the rate of hydration of CO₂ plays an insignificant role in the exchange mechanisms between the atmosphere and the oceans.     

LiTi2(PO4)3的Na/Li离子交换特征

锂离子传导材料LiTi₂(PO₄)₃能在LiCl水溶液中高选择性地与Na⁺进行离子交换. 研究了NaCl 溶液中LiTi₂(PO₄)₃上的Na/Li离子交换反应, 实验结果表明, 升高温度能显著提高LiTi₂(PO₄)₃上的Na/Li交换反应速率, 其离子交换动力学规律可近似由JMAK(Johnson-Mehl-Aurami-Kalmogorav)方程描述. 对LiTi₂(PO₄)₃在水和NaCl溶液中的溶解行为的研究结果表明, 升高温度能加快其在水中的溶解速率, pH值过大或过小及离子交换都会加剧LiTi₂(PO₄)₃的溶解.